CN106497215B

CN106497215B - Application of eugenol polyether and eugenol polyether siloxane as wetting agent

Info

Publication number: CN106497215B
Application number: CN201610757920.7A
Authority: CN
Inventors: K·罗兰; M·勒贝特; M·费伦茨; T·席勒
Original assignee: Evonik Operations GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2015-09-03
Filing date: 2016-08-29
Publication date: 2021-06-29
Anticipated expiration: 2036-08-29
Also published as: EP3138867A1; US20170065951A1; US9993786B2; BR102016020031A2; CN106497215A; EP3138867B1

Abstract

The present invention relates to compositions comprising eugenol polyethers and/or siloxane-modified eugenol polyethers, and the use of eugenol polyethers and polyether siloxanes based on these eugenol polyethers as wetting agents.

Description

Application of eugenol polyether and eugenol polyether siloxane as wetting agent

Technical Field

Background

Aqueous inks and varnishes are used industrially on a large scale. A key factor for good wetting of the substrate is the reduction of the surface tension of the aqueous system with the aid of surfactants. Here, it is not only critical that the static surface tension is reduced to a lower value, but also that the dynamic surface tension. More specifically, for fast application, for example in the spraying of paints, or in the printing process, low dynamic surface tensions are required. Furthermore, the surfactants used must not disrupt the formation of a uniform film and cause any turbidity, and should also be low-foaming, i.e. not promote the accumulation of large amounts of foam.

Especially in the case of the use of such surfactants in the field of printed food packaging, there is a very high demand for the ability of the substances used to migrate into the food. In order to avoid that such substances are absorbed into the human body, the substances must have little, if any, migration potential. The synthesis of such surfactants therefore requires a very specific choice of raw materials. Even the essential components should be toxicologically safe. It is particularly important that the starting materials are non-toxic even in small amounts and exhibit low migration levels to the food product if they are not completely converted to surfactants in the reaction and thus remain present in the product.

The wetting agents known from the prior art usually meet the criteria of food compatibility and low migration only to a limited extent, if at all.

A frequently used class of surfactants are fluorosurfactants. It is characterized by a very significant reduction in static surface tension, but a significant tendency to foam. For example, DE 102011052991B 4 describes the use of fluorosurfactants to wet difficult-to-wet printing plates in dry offset printing. DE 102009032615 a1 describes the use of fluorosurfactants in the formulation of writing inks, which can be used on easy-to-clean surfaces, i.e. those that are also difficult to wet. Only recently, the use of fluorinated surfactants has been greatly limited. Perfluorinated Surfactants (PFTs) have been detected everywhere and are found in drinking water in particular. The half-life of these substances in the human body is long, resulting in accumulation in the organism.

Another class of surfactants often used is based on acetylenic diols and alkoxylates thereof. With these surfactants, static and dynamic surface tensions can be reduced, but the values achievable do not fully reach those of non-ionic and anionic surfactants. On the other hand, formulations containing these surfactants are relatively low foaming (EP-B-0897744, US-2997447). For example, WO 2014/098001 a1 describes the use of acetylenic surfactants in, for example, ink jet printing inks.

The problem is the (eco) toxicological evaluation of products based on 2,4,6, 8-tetramethyl-5-decyndiol. These products cause severe eye irritation, are classified as eye contact sensitive, and accumulate in water. The only product available to paint manufacturers from this class of materials is a solid product, or the material, for ease of handling, is provided as a 50% solution in a variety of solvents such as ethylene glycol (classified as a hazardous health, suspected teratogen).

In addition, ethoxylates of octylphenol or nonylphenol or ethylene oxide-propylene oxide copolymers are used as surfactants for reducing the surface tension. For example, US 2014/0078217 a1 describes the use of nonylphenol ethoxylates to print fixative solutions to non-porous surfaces.

However, also in the case of such surfactants, the results of ecotoxicological studies have to be taken into account. It has been demonstrated that the reactants of the ethoxylate surfactants used, i.e. octylphenol and nonylphenol, interfere with the hormone metabolism of fish. Accordingly, the starting materials, as well as the surfactants themselves, are classified as water contaminants and have been banned in many applications. The use of these substances in varnishes and inks is still currently permitted. However, due to various regulations, its use in printed food packaging has been banned.

Disclosure of Invention

It is therefore an object of the present invention to provide wetting agents which meet the stringent requirements for food-contact additives, which are at the same time stable, homogeneous compounds and can be used in particular as substrate wetting agents.

It has surprisingly been found that eugenol-based polyethers, hereinafter also referred to as eugenol polyethers, and polyether siloxanes prepared therefrom meet all the requirements stated and have excellent suitability as wetting agents. According to the invention, "eugenol-based polyether" is understood to mean a polyether comprising at least three alkoxy units and prepared using eugenol as alcohol starting material. The preparation thereof is described in a patent application which has not yet been published, reference being made to DE 102014217790.1. DE102014217790.1 is hereby incorporated by reference and is considered to form part of the disclosure of the present patent application.

For example, surfactant polyethers based on aromatic alcohols (i.e. phenols) as starting materials are well known, for example as described in US 5296627 and US 6646091B 2.

Documents EP 94386B 1 and DE 3342509 a1 describe compositions comprising polyethers based on eugenol.

The base-catalyzed alkoxylation of eugenol is described in detail for the first time in EP 1717259 a 1. In the examples reported therein, eugenol is charged first as starting material and then mixed with a basic catalyst, for example sodium methoxide. After removal of methanol from the catalytic step, ethylene oxide, propylene oxide and/or butylene oxide are added at a temperature of 140 ℃ and 160 ℃. This procedure provides unambiguously pure iso-eugenol-based polyethers, meaning that in an alkaline alkoxylation process the eugenol allyl groups undergo quantitative rearrangement to form 2-propenyl groups. The resulting structural units are known to the person skilled in the art under the name of isoeugenol. There is no description of the use of such eugenol polyethers as wetting agents.

Polyether siloxanes with eugenol groups are known in principle from the scientific literature. In these cases, the term "polyether siloxane" derives from the fact that: in general, not only eugenol but also conventional terminally unsaturated polyethers (e.g. alkoxylates of allyl alcohol) are hydrosilylated to SiH-bearing alkylpolysiloxanes, in individual cases also with other terminally unsaturated compounds, e.g. olefins. As described in EP 1010748B 1, EP 887367 A3 and EP 845520B 1, for example, eugenol-containing polyether siloxanes are used as diesel defoamers. The use as wetting agents has not been described before.

In terms of process engineering, a disadvantage of the prior art processes for preparing polyether siloxanes having eugenol groups and polyether groups by hydrosilylation is that two or more unsaturated products have to be added simultaneously to the SiH-bearing polyether siloxanes. Since the reactants to be added (e.g. eugenol and polyethers) (as well as the natural SiH-bearing polysiloxanes) differ significantly in their molecular weight as well as in their hydrophilicity/hydrophobicity, it is difficult to prepare compositionally consistent polyether siloxanes in which the different reactants are distributed uniformly throughout the siloxane chain. Thus, inadequate mixing very rapidly leads to products of inhomogeneous composition and this must be avoided for quality and cost reasons.

In the wetting agents of the invention, it is already possible to combine the aromaticity of the hydrosilylatable eugenol with the flexibly adjustable hydrophilicity/hydrophobicity of the polyether in one molecule/polymer.

The pure polyether-based wetting agent used can in principle be any eugenol polyether prepared by any prior art process. The eugenol polyethers hydrosilylated to SiH-bearing polysiloxanes to give eugenol polyether siloxanes are preferably prepared by transition metal-catalyzed alkoxylation of eugenol, particularly preferably by double metal cyanide catalysis. The reason for this is that base-catalyzed alkoxylation of eugenol has been shown to result in polyethers based on isoeugenol (see below), which are not hydrosilylatable.

Considering that also the isoeugenol polyether obtained by base-catalyzed alkoxylation of eugenol meets the requirements of the present invention, the expression "eugenol polyether as wetting agent" in the following text explicitly also includes the isoeugenol structure without requiring any explicit specification in the corresponding text paragraph.

In the context of the present invention, the term "alkoxylation products" or "polyethers" includes not only polyethers, polyether alcohols (polyether alcohols) and polyether ester alcohols (polyether esters), but also polyether carbonate alcohols, which may be used synonymously with one another. Also, the term "poly" does not necessarily imply that there are multiple ether or alcohol functions in a molecule or polymer. Rather, this merely means that at least a single repeating unit of monomer units is present, or that the composition has a relatively high molar mass and an additional polydispersity.

In the context of the present invention, the word "poly" includes not only compounds having at least 3 repeating units of one or more monomers in the molecule, but also in particular compositions of compounds which have a molecular weight distribution and at the same time an average molecular weight of at least 200 g/mol. This definition takes into account the fact that: these compounds are often referred to as polymers in the industry concerned, even if they do not meet the polymer definition according to OECD or REACH regulations.

Accordingly, the term "eugenol-based polyether" does not only describe alkoxylates but also includes eugenol reaction products in which, in addition to alkylene oxides, further (co) polymerizable monomers are converted by ring opening, which are explained in detail below.

The present invention provides the use of eugenol-based polyethers and/or eugenol-based polyether siloxanes, in particular of the compounds of the formulae (I) and/or (II) described hereinafter, as wetting agents, in particular as substrate wetting agents.

The invention likewise provides compositions comprising the compounds of the formulae (I) and/or (II) described below, and their use as wetting agents, in particular as substrate wetting agents.

Detailed Description

The subject matter of the invention is described by the following embodiments without any intention to limit the invention to these exemplary embodiments. When ranges, general formulae or classes of compounds are specified below, these shall include not only the corresponding ranges or classes of compounds explicitly mentioned, but also all subranges or subgroups of compounds which can be obtained by extracting individual values (ranges). When a document is referred to in the context of this specification, its content, particularly with respect to the subject matter that forms the context in which it is referred to, is deemed to form part of the disclosure of the invention in its entirety. When chemical (empirical) formula is used in the present invention, the reported index may be not only absolute number but also average value. The index relating to the polymeric compound is preferably an average value. Percentages are by weight unless otherwise indicated. If the measurements are reported below, these measurements have been carried out under standard conditions (25 ℃ and 1,013mbar) unless otherwise indicated. When an average is reported below, the values referred to are weight averages unless otherwise indicated.

Preference is given to the use of eugenol-based polyethers and/or eugenol-based polyether siloxanes, in particular of the formulae (I) and/or (II), as substrate wetting agents in printing inks, printing varnishes and other coatings, varnishes, inks, colour preparations (colour preparation) or coatings applied by analogue or digital coating methods.

It has been found that the eugenol-based polyethers and/or eugenol-based polyether siloxanes according to the invention, in particular those of the formulae (I) and/or (II), are particularly suitable as substrate wetting agents in printing inks, printing varnishes and other coatings, varnishes, inks, colour formulations or coatings applied by analogue or digital coating methods.

The compounds according to the invention are particularly suitable as substrate wetting agents for printed films, paper, cards, cardboard, folding boxes, pouches (pouch), bags, wallpaper, sacks (sack), hygiene paper (hygene paper), labels, beverage cartons, boards, wood surfaces, metal surfaces, plastic surfaces, glass and/or ceramics.

Very good results can be achieved in the context of products used in the food industry, such as packages made of paper and paperboard packages and consumer products.

In particular, these include:

single-and multi-ply qualities of corrugated board (e.g. flute (e.g. A, B, C or E-flute) for industrial and artistic/creative sectors using a variety of different linerboards (e.g. imitation paper, brown board, kraft paper, test liner and single-or multi-ply coated and single-or multi-ply qualities, such as GD2 or Kemiart Ultra)),

folding boxes (e.g. of single-coated quality for packaging dry food, pharmaceutical and other dry goods; of double-coated and/or laminated quality for moist, greasy or oily goods (e.g. frozen food or fat)),

bags (e.g. bread bags, paper shopping bags, single-and multi-layer bags for dry, damp and greasy goods),

sacks (e.g. single-or multi-layer sacks for goods such as cement, cat litter, seeds or dry feed),

hygiene papers (such as napkins, kitchen papers, toilet papers and toilet tissues, also including wet wipes and impregnated pads),

beverage cartons (e.g. from

SIG

Or

And a package of) and

-other aseptic cardboard packaging.

Also, packages and consumer products made of plastic are preferably used. These include in particular:

packaging films (e.g. PE, PP, OPP, BOPP, PET, PEN (polyethylene naphthalate, e.g. polyethylene naphthalate)

) Polyesters (e.g. of the formulae

Or

) Cellulose hydrate film

PVC (polyvinyl chloride) and includes "biofilms", such as PLA (polylactic acid), in monolayer form or as multilayer composites (also known as laminates),

protective, separating, decorative films (e.g. from Konrad Hornschuch AG)

) Carrier films, transfer films, protective films, diaper films, medical films, functionalized films, and other films commonly used,

rigid plastic materials, such as plastic sheets (e.g. available from Evonik Industries AG)

Polycarbonate sheets, e.g.

PVC sheets, etc.).

Furthermore, the use on metal substrates is also possible and preferred. This includes, inter alia, aluminium foils or aluminium-containing composite materials (e.g. as lids for yoghurt pots, lids for ready-to-eat food and animal nutrition, packaging for medical products andsimilar packaging) and composite sheets (e.g. of the type

) And metal sheets (for metal packaging such as cracker cans, labels, metal panels, and similar consumer goods).

Furthermore, it is also likely and preferred for use in the building and furniture industries, particularly in sheeting such as veneer (e.g., under the trade name brand name)

Or

(high pressure laminate) or

(available from fiber cement boards), sheets and panels for interior and exterior applications (e.g. GFRP (glass fiber reinforced plastic)),

Panels made of composite material or plastic (e.g. PVC (polyvinyl chloride) panels from Deceuninck), dry construction panels (e.g. plasterboard (e.g. Rigips panels from Saint-Gobain Rigips GmbH or Drystar panels or from Knauf Gips KG)

) Gypsum fiberboard (e.g., available from Fermacell GmbH

) And others such as gypsum blocks and plasters (screened elements)), laminate flooring (e.g. decorative MDF boards (medium density fibreboard) available from Kronotex) and a number of different sheet types for furniture and interior finishing (MDF, OSB (oriented strand board), plywood (board made of glued veneer layers), composite boards (concrete form of plywood with different thickness and strength added veneer layers), screen printing boards (concrete form of plywood with phenolic resin coating and embossed by screen printing)Patterned plywood), laminated wood (glued and partially joggled solid wood panels), etc.).

Furthermore, use on glass and ceramic surfaces is also possible and preferred. These include, inter alia, bottles, glasses and other containers of glass and ceramic materials (e.g. vessels or industrial ceramics, such as insulators or crucibles for high temperature applications), as well as many different types of flat glass and planar ceramic materials (e.g. flat glass (flat or in many different curvatures), ceramic tiles, industrial ceramics, such as heat-resistant bricks), safety glass (e.g. glass, ceramic, glass-ceramic, ceramic-ceramic

Or bullet resistant glass) as well as a variety of different tempered or coated glasses and ceramics, including specifically industrial glasses (e.g., spectacle glasses, lenses, panes, etc.).

Furthermore, use in cosmetics is possible and preferred, for example nail varnishes, and in inks, Indian inks and other colour formulations, or in applications using writing instruments such as pens, plotters, felt pens, ball point pens and the like.

Other possible and preferred are the use in coatings, inks, indian inks and other paint or varnish applications applied by industrial and artistic methods such as dipping, spraying, rolling, brush application, die application, spray gun, casting etc.

In addition, the eugenol-based polyethers and/or eugenol-based polyether siloxanes according to the invention are suitable for use in products in which, for example, on account of contact with children, use of safe raw materials is preferred (according to DIN EN 71-3 and attributes).

The eugenol-based polyether of the invention preferably has the structure shown in formula (I):

wherein

a is from 1 to 1,000, preferably from 2 to 500, more preferably from 3 to 500, even more preferably from more than 3 to 100, particularly preferably from 4 to 50,

b is from 0 to 1,000, preferably from 1 to 500, more preferably from more than 1 to 200, particularly preferably from 0 to 50,

c is from 0 to 1,000, preferably from 1 to 100, more preferably from more than 1 to 80, particularly preferably from 0 to 50,

d is 0 to 1,000, preferably 1 to 100, more preferably greater than 1 to 80, particularly preferably 0 to 50,

e＝1-10，

f is 0 to 500, preferably 1 to 300, more preferably 2 to 200, and particularly preferably 0 to 100,

provided that the sum of a + b + c + d + f is not less than 3, and

with the proviso that the radicals with indices a, b, c, d and f can be freely transposed throughout the molecular chain, and neither radical with indices c and d can follow either itself or the other,

and provided that the different monomer units and the segments with indices a, b and f can be in block structure with one another, wherein the individual blocks may also be repeated a number of times and may be randomly distributed with respect to one another or randomly distributed and also freely transposed with respect to one another, in the sense that they can be arranged in any desired order, with the proviso that the groups with indices c and d cannot follow one another or follow one another in both,

and wherein

R¹Hydrogen or alkyl radicals having 1 to 8 carbon atoms, independently of one another, preferably hydrogen, methyl or ethyl, particularly preferably hydrogen,

R²hydrogen, alkyl radicals having from 1 to 20 carbon atoms, or aryl, or alkylaryl radicals, independently of one another, preferably hydrogen, methyl, ethyl, octyl, decyl, dodecyl, phenyl, benzyl, more preferably hydrogen, methyl or ethyl, or

R¹And a R²The radicals may together form a ring including R¹And R²Bonded atoms, the ring preferably containing 5 to 8 carbon atoms,

R³saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30Carbon atoms, in particular not more than 24 carbon atoms, optionally with further substitutions,

for example, R³It may also contain silyl, alkoxysilyl or carboxylate groups, for example dialkoxyalkylsilyl or trialkoxysilyl groups, preferably trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl or diethoxymethylsilyl groups,

R⁴、R⁷hydrogen and/or organic radicals, independently of one another, preferably alkyl, alkenyl, alkylidene, alkoxy, aryl and/or aralkyl radicals, or R⁴And/or R⁷Optionally absent, wherein, when R is⁴And R⁷When not present, in R⁴And R⁷The position of the group is replaced by a C ═ C double bond,

the bridging Z-fragment may be present or absent,

wherein, in the absence of a bridging Z-fragment,

R⁵、R⁶hydrogen and/or organic radicals, independently of one another, are preferably alkyl, alkenyl, alkylidene, alkoxy, aryl and/or aralkyl radicals, where, when R is present⁴And R⁷When one of the groups is absent, the corresponding paired group (i.e. when R is present⁴Is absent is R⁵And R⁷In the absence of R⁶) Is alkylidene, preferably methylidene (═ CH)₂)；

Wherein, in the presence of the bridging Z segment,

R⁵、R⁶a hydrocarbyl group bridged cycloaliphatic or aromatic by a Z segment, wherein Z is a divalent alkylene or alkenylene group, which may be further substituted,

R⁸、R⁹hydrogen, alkyl, aryl or alkylaryl groups having from 1 to 20 carbon atoms and/or alkoxy groups, independently of one another, preferably methyl groups,

R¹⁰hydrogen or alkyl or ester groups having 1 to 8 carbon atoms-c (o) -R independently of one another¹¹Or acetoacetic acidEster group-C (O) -CH₂-C(O)-R¹²Or a silyl ether group-Si (R)¹³)₃Or a carbamate group-C (O) -N- (R)¹⁴)₂OR a phosphate group-P (O) - (OR)¹⁹)₂Wherein

R¹¹、R¹²、R¹³Linear or branched, saturated or unsaturated, optionally further substituted alkyl, aryl or alkylaryl groups having from 1 to 30 carbon atoms, and

R¹⁴independently of one another, hydrogen and/or linear or branched, saturated or unsaturated, optionally further substituted alkyl, aryl or alkylaryl groups having from 1 to 30 carbon atoms, and

R¹⁸independently of one another, an allyl or 2-propene group, and

R¹⁹hydrogen, alkyl radicals, independently of one another, preferably having from 1 to 30, in particular from 1 to 20, carbon atoms, or polyether radicals,

R¹⁰preference is given to hydrogen, methyl groups, acetyl groups, phosphate groups or acetoacetate groups, particular preference to hydrogen or phosphate groups.

The eugenol-based polyether of formula (I) preferably has segments wherein at least one subscript is a, more preferably segments wherein at least two different subscripts are a.

The starter for the transition metal-catalyzed and DMC-catalyzed alkoxylation reaction is preferably eugenol, which makes it possible to obtain products of the formula (I) in which R is¹⁸An allyl group.

The starting materials for the base-catalyzed alkoxylation reaction are preferably eugenol and isoeugenol, which makes it possible to obtain products of the formula (I) in which R is¹⁸2-propenyl group.

Eugenol (CAS number: 97-53-0) is an allyl-substituted phenol known by the chemical names 4-allyl-2-methoxyphenol, 4-prop-2-enyl-2-methoxyphenol, 4-allylcatechol-2-methyl ether, and 5-eugenol. Eugenol is a natural raw material, and takes clove oil and pepper oil as main components. Eugenol can be obtained from aqueous alkaline treatment (extraction) of clove oil. From an ecological point of view, the sustainable source of eugenol raw material and the corresponding avoidance of petrochemical raw materials are considerable advantages, especially when considering that eugenol does not compete with any food use.

Isoeugenol (CAS number: 97-54-1) is a structural isomer of eugenol in which the allyl group has been rearranged to the 2-propenyl group. Isoeugenol is typically prepared by the isomerization of eugenol. The compounds of the formula (I) are therefore preferably prepared from eugenol, since for economic and ecological reasons, an additional work-up step of isomerization is preferably not required.

Alkylene oxides which can generally be used include all alkylene oxides known to the person skilled in the art and those which can be used in pure form or in any desired mixtures. Examples of useful oxyalkylene compounds for obtaining the segment designated in formula (I) with the subscript a include ethylene oxide, 1, 2-propylene oxide (propylene oxide), 1, 2-epoxy-2-methylpropane (isobutylene oxide), epichlorohydrin, 2, 3-epoxy-1-propanol, 1, 2-butylene oxide (butylene oxide), 2, 3-butylene oxide, 2, 3-dimethyl-2, 3-butylene oxide, 1, 2-pentylene oxide, 1, 2-epoxy-3-methylpentane, 1, 2-hexylene oxide, 1, 2-cyclohexylene oxide, 1, 2-heptylene oxide, 1, 2-octylene oxide, 1, 2-nonylene oxide, 1, 2-decylene oxide, 1, 2-epoxyundecane, 1, 2-epoxydodecane, styrene oxide, 1, 2-epoxycyclopentane, 1, 2-epoxycyclohexane, vinylcyclohexene oxide, (2, 3-epoxypropyl) benzene, vinylethylene oxide, 3-phenoxy-1, 2-epoxypropane, 2, 3-epoxymethyl ether, 2, 3-epoxyethyl ether, 2, 3-epoxyisopropyl ether, butyl 3, 4-epoxystearate, 4, 5-epoxyacetic acid pentyl ester, 2, 3-epoxypropane methacrylate, 2, 3-epoxypropane acrylate, glycidyl butyrate, methyl glycerate, 2, 3-epoxyethyl butyrate, 4- (trimethylsilyl) butane-1, 2-epoxide, 4- (triethylsilyl) butane-1, 2-epoxide, 3- (perfluoromethyl) -1, 2-epoxypropane, 3- (perfluoroethyl) -1, 2-epoxypropane, 3- (perfluorobutyl) -1, 2-epoxypropane, 3- (perfluorohexyl) -1, 2-epoxypropane, 4- (2, 3-epoxypropyl) morpholine, 1- (oxiran-2-ylmethyl) pyrrolidin-2-one. Preference is given to using ethylene oxide, propylene oxide, butylene oxide and styrene oxide. Particular preference is given to using ethylene oxide and propylene oxide. In a very particularly preferred embodiment, ethylene oxide and propylene oxide are used in a molar ratio of from 1:3 to 3:1, preferably from 1:2 to 2:1, particularly preferably from 1:1.5 to 1:1.

The glycidyl ethers which can be used and which give the segment with the subscript b specified in formula (I) generally include all glycidyl ethers known to the person skilled in the art, either in pure form or in any desired mixture.

Preferably methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2-dimethylpropyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl (2-butyloctanyl), 2-methylundecyl, 2-propylnonyl, 2-ethyldecyl, 2-pentylheptyl, 2-hexyldecyl, 2-butyltetradecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, 3,5, 5-trimethylhexyl, isononyl (isononanyl), isotridecyl, isomyristyl, iso-myristyl, Isostearyl, 2-octyldodecyl, trityl, -C (O) - (CH)₂)₅-C-(CH₃)₃(residue of neodecanoic acid), C₁₂/₁₄Alkyl, phenyl, tolyl, tert-butylphenyl or benzyl glycidyl ether, and 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltriisopropoxysilane, bis (3-glycidoxypropyl) dimethoxysilane, bis (3-glycidoxypropyl) diethoxysilane, 3-glycidoxyhexyltrimethoxysilane, 3-glycidoxyhexyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane. It may be particularly preferable to use 2-ethylhexyl glycidyl ether, neodecyl glycidyl ether, C₁₂/C₁₄Alkyl glycidyl ethers, cresyl glycidyl ether and tert-butylphenyl glycidyl ether, and very particular preference is given to using tert-butylphenyl glycidyl ether or cresyl glycidyl ether.

Glycidyl ethers which may be used also include polyfunctional glycidyl ethers, such as 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycerol-3-glycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether or pentaerythritol tetraglycidyl ether, with the aid of which it is also possible to introduce branched structures into the alkoxylated end product of the formula (I).

To introduce the segment designated in formula (I) with the subscript c into the polyether, a reaction with CO may be carried out₂Copolymerization of (2).

The cyclic anhydrides which can be used and which give the segment of formula (I) designated by the subscript d generally include all cyclic anhydrides known to those skilled in the art, either pure or in any desired mixture. Saturated, unsaturated or aromatic cyclic dicarboxylic anhydrides which may be preferably used include: succinic anhydride; oct (en) -yl-, dec (en) -and dodec (en) succinic anhydride; maleic anhydride; itaconic anhydride; glutaric anhydride; adipic anhydride; citraconic anhydride; trimellitic anhydride; phthalic anhydride; hexahydro-, tetrahydro-, dihydro-, methylhexahydro-, and methyltetrahydrophthalic anhydride; and also polyfunctional acid anhydrides such as pyromellitic dianhydride, benzophenone-3, 3',4,4' -tetracarboxylic dianhydride, 1,2,3, 4-butanetetracarboxylic dianhydride; and homopolymers or copolymers of maleic anhydride with ethylene, isobutylene, acrylonitrile, vinyl acetate or styrene by free-radical polymerization.

Succinic anhydride, maleic anhydride, phthalic anhydride and hexahydrophthalic anhydride, in particular maleic anhydride and phthalic anhydride, are particularly preferred.

Lactones which can be used and which lead to the fragment designated in formula (I) having the subscript f generally include all lactones known to the person skilled in the art, either in pure form or in any desired mixture.

Preferably valerolactone or caprolactone, each of which may be unsubstituted or substituted by an alkyl group, preferably a methyl group. Preferably epsilon-caprolactone or delta-valerolactone, in particular epsilon-caprolactone.

Alkoxylation of OH-functional starter compounds can be carried out under base, acid or transition metal catalysis. As mentioned at the outset, the alkoxylation of eugenol is preferably carried out in the presence of Double Metal Cyanide (DMC) catalysts if the aim is to convert the eugenol into a polyether siloxane again by hydrosilylation.

The preparation and use of DMC catalysts for alkoxylation reactions has been known since the 60's of the 20 th century and is outlined, for example, in US 3,427,256, US 3,427,334, US 3,427,335, US 3,278,457, US 3,278,458 and US 3,278,459. In the meantime, more effective DMC catalysts, in particular zinc-cobalt hexacyano complexes, have been developed, for example in US 5,470,813, US 5,482,908 and EP 1276563B 1.

The double metal cyanide catalysts (DMC catalysts) used are preferably those described in EP 1276563B 1, in particular the DMC catalysts described therein as preferred or particularly preferred.

The hydroxyl-terminated groups of the eugenol-based polyether may remain in free form or may be partially or completely modified to optimize the compatibility of the substrate for later use.

Possible modifications include not only further condensation or addition reactions, for example with isocyanates, but also transesterification, esterification and etherification.

The esterification reaction can be carried out with organic or inorganic acids or their corresponding anhydrides. In the case of the use of polyhydroxyfunctional acids, such as phosphoric acid, the esterification can in principle be carried out at any free OH group, according to the reaction scheme, which can thus result in the bonding of two or three eugenol-based polyethers according to the invention via the phosphoric acid group and thus in the formation of the corresponding diesters or triesters. Preferably, in particular cases, the reaction scheme is chosen so as to form predominantly the monophosphates of the eugenol-based polyether of the invention.

The chemical modification of the free hydroxyl groups of the eugenol-based polyether can be carried out with SiH-functional polysiloxanes before or after the hydrosilylation reaction.

The polydispersity (Mw/Mn) of the eugenol based polyether of formula (I) determined by GPC is preferably <2.5, more preferably <2.0, and more preferably >1.05 to < 1.5.

In addition to the eugenol polyethers of the formula (I), it is also possible to use polyether siloxanes of the general formula (II) as wetting agents.

Preferably, the polyether siloxanes of the general formula (II) can be obtained by noble metal-catalyzed hydrosilylation of eugenol polyethers of the formula (I) with SiH-functional siloxanes, forming SiC bonds of the polyethers with the siloxanes.

The SiH functional siloxane may preferably be provided by carrying out an equilibration of prior art processes, preferably by sulfonating the resin. The equilibration of branched or linear, optionally hydrosilylated poly (organo) siloxanes having terminal and/or pendant SiH functions is described in the prior art, for example in documents EP 1439200 a1, DE 102007055485 a1 and DE 102008041601. These documents are incorporated herein by reference and are considered to form part of the disclosure of the present invention.

The preparation of the preferably used silicone polyether block copolymers can be carried out by methods of the prior art, in which branched or linear polyorganosiloxanes having terminal and/or pendant SiH functions are reacted with an unsaturated polyether or a polyether mixture consisting of at least two unsaturated polyethers. The reaction is preferably carried out as a noble metal-catalyzed hydrosilylation, as described, for example, in EP 1520870. As in the as yet unpublished application DE102014217790.1, document EP 1520870 is hereby incorporated by reference. The noble metal catalyst used is preferably a platinum-containing catalyst.

In addition to these, it may be advantageous in the preparation of the polyether siloxanes preferably used as wetting agents to convert other linear and/or branched unsaturated polyether compounds, similarly treating other terminally unsaturated organic compounds, together with terminally unsaturated eugenol polyethers. This may be particularly advantageous for adjusting the compatibility of the eugenol polyether-containing polysiloxane with the substrate for a particular application.

Advantageously, this polyether is an allyl polyether obtainable by any of the prior art methods.

Such terminally unsaturated organic compounds are preferably alkene or alkyne compounds, which may carry further substituents. For example, it is possible to use allyl glycidyl ether, monoallyl glycidyl ether, allyl anisole, allyl phenol, eugenol, hexenol, hexadecene and methyl undecylenate (methyl undecylenoate), with hexadecene, eugenol and monoallyl glycidyl ether being particularly preferred.

Advantageously, the useful polyethersiloxanes may contain exclusively eugenol-based polyethers or any desired mixtures of these eugenol-based polyethers with terminally unsaturated compounds. The molar ratio of the unsaturated eugenol-based polyether to the unsaturated compound used is preferably from 0.001 to 100 mol%, more preferably from 10 to 100 mol%, particularly preferably from 20 to 80 mol%, relative to the sum of the eugenol-based polyether and the unsaturated compound.

The polysiloxane compounds of formula (II) of the present invention:

M_g M‘_h M“_n D_i D’_j D”_m T_k Q_lformula (II)

Is that:

M＝[R¹⁵ ₃SiO_1/2]

M’＝[R¹⁶R¹⁵ ₂SiO_1/2]

M”＝[R¹⁷R¹⁵ ₂SiO_1/2]

D＝[R¹⁵ ₂SiO_2/2]

D‘＝[R¹⁶R¹⁵SiO_2/2]

D“＝[R¹⁷R¹⁵SiO_2/2]

T＝[R¹⁵SiO_3/2]

Q＝[SiO_4/2]

g is 0 to 20, preferably 0 to 10, particularly preferably 2,

h is 0 to 20, preferably 0 to 10, particularly preferably 0,

i is from 0 to 1,000, preferably from 0 to 500, particularly preferably from 0 to 200,

j is from 0 to 20, preferably from 1 to 15, particularly preferably from 1 to 10,

k is 0 to 20, preferably 0 to 10, particularly preferably 0,

l is from 0 to 20, preferably from 0 to 10, particularly preferably 0,

m is 0 to 20, preferably 1 to 15, particularly preferably 0,

n is 0 to 20, preferably 0 to 10, particularly preferably 0,

provided that the sum of g + h + i + j + k +1+ m is not less than 3 and the sum of h + j is ≧ 1,

and is

R¹⁵Independently of one another, identical or different hydrocarbyl radicals having 1 to 16 carbon atoms or H, preferably methyl, ethyl or phenyl, particularly preferably methyl,

R¹⁶with the proviso that at least 10% of the radicals are eugenol-based polyether radicals, which preferably correspond to the general formula (III)

And preferred polyethers not based on eugenol correspond to a group of the general formula (IV):

wherein the subscripts a to f and the group R¹-R¹⁰The definition of (a) is as described above,

R¹⁷independently of one another, identical or different hydrocarbon-based radicals having from 1 to 16 carbon atoms and which may also contain heteroatoms and may have further substitutions, preferably SiC-bonded radicals from allyl glycidyl ether, monoallyl glycidyl ether, allyl anisole, eugenol, hexenol, hexadecene and methyl undecylenate, particularly preferably SiC-bonded radicals from hexadecene, eugenol and monoallyl glycidyl ether.

The compounds of the general formula (II), which, together with the eugenol-based polyethers of the formula (III), also contain polyethers of the formula (IV) which are not eugenol-based, are advantageously used in these systems which require a compatibility adjustment. If the polyether siloxane contains only eugenol-based polyether structures, any necessary adjustment of the compatibility can also be achieved by the intrinsic structure of the eugenol-based polyether.

The silicone compounds of the invention can preferably be obtained by the process described in DE 102014217790.1.

As already mentioned, the use of eugenol-based polyethers and/or polyether siloxanes as wetting agents, preferably as substrate wetting agents, is envisaged according to the invention.

The substrate wetted with the product of the invention can in principle be any printable and coatable substrate known to the person skilled in the art. This includes flexible and rigid substrates.

The substrates mentioned hereinafter are intended to be better illustrated and are particularly preferred, but should not be considered as being limited to these particular substrates.

In these applications, suitable substrates include a wide variety of qualities that are used in a wide variety of end uses that are common in the marketplace.

In the final use of corrugated board, these are non-coated papers such as kraft liners, test liners and imitation papers. In these paper qualities, the printability of linered paper is significantly affected by the proportion and quality of the waste paper used in the production. In particular, qualities with a high proportion of unsorted waste paper, as is customary in the case of imitation paper, require substrate wetting agents which have a specific effect on the cleaning print in order to reliably balance out the uneven surface tension of the substrate.

Furthermore, in the case of corrugated board, especially for high quality packaging, coated paper, such as coated kraft liner (e.g., available from

Kemiart Ultra quality) and coated test pads (e.g., topiliner GD2, supplied by manufacturers such as Papyrus). Of these typesThe coating of paper affects two key parameters of printing: absorption rate and surface tension. The reduction in absorption and surface tension makes uniform wetting difficult, which in turn requires the use of substrate wetting agents with specific effects.

Furthermore, in the case of corrugated cardboard, paper products coated with plastics, for example PE or PET, are used for specific applications, for example for the packaging of dough and other baking materials, or moisture-sensitive products, such as powders. Furthermore, paper quality provided with a protective coating (such as a grease protective coating available from X300 of Michelman) can also be used for the production of secondary packaging for greasy products (such as cooking grease). In particular, in the case of such substrates, for uniform wetting of the substrates, substrate wetting agents are required which have good efficacy and preferably low mobility for applications in the field of food packaging.

In the end use of folding boxes and similar cardboard packaging, coated paper and card qualities are mainly used. The requirements for printability and the substrate wetting agent used are similar to those described for the end use of corrugated board.

In the end use of pouches and bags, it is common to use a composition having a weight of less than 100g/m²Kraft paper and soda paper of grammage. These are usually applied only in small amounts, if at all, and are compacted by calendering. The printing characteristics are similar to those of coated papers used in the production of corrugated paper. Due to the high regulatory requirements for the color fastness of packaging bags such as bread bags (bakers 'bag) and meat bags (butchers' bag), for which long term contact fastness according to DIN EN 646 is necessary, the requirements in terms of prescribed effectiveness and minimum migration potential are particularly high in the case of paints and varnishes for these packaging materials. This requires the use of substrate wetting agents optimized in this respect.

In the end use of sacks packaging, a variety of uncoated and coated papers are used as linered papers. Sacks, also known in the industry as rectangular sacks (sack sacks), have a multilayer structure consisting of various paper and/or plastic layers, depending on their nature and the specific weight of the goods. The linered paper and the requirements for printing inks and printing varnishes for printing vary according to the goods to be packaged. In particular, in the case of commercial products such as animal dry feed or seeds, again, high demands are made on the non-migration of the ingredients used. Furthermore, the high requirements in terms of abrasion resistance, blocking resistance and surface slip resistance pose a great challenge to the performance of the substrate wetting agent, since these properties are closely linked to the uniformity of the applied paint or varnish film.

In the end use of newspapers, a variety of generally uncoated papers are used as linerboards, as well as coated papers. In printing, the wetting agent is used when a method such as flexographic printing, gravure printing, screen printing, or digital printing (e.g., inkjet printing) is used. In such end uses, the challenge for substrate wetting agent performance lies firstly in the speed of substrate wetting (which is a quality determining factor, especially in the case of very high speed printing machines which can be up to speeds of 1,000 meters per minute), and secondly in the precise control of substrate wetting. This is of crucial importance, especially in the case of uncoated or only lightly coated paper quality, since excessive wetting can lead to uncontrolled flow of printing ink or printing varnish and thus to poor printed images. In the case of coated and highly coated paper qualities, there is again a risk of printing failure as a result of insufficient wetting of the substrate. Another aspect is the recyclability of the printing paper. High molecular weight substrate wetting agents with positive properties with respect to migration potential make a positive contribution to the improvement of quality and extend the possible uses of the substrate quality produced with recycled materials.

For end uses of form printing and pinstripe inks, paper of the respective quality, usually a small amount of coating, is used. However, in the case of products from the low-cost section, uncoated paper is also used, and for high-quality forms and writing materials, coated paper and calendered paper are also used as the base material. Printing is often performed by flexographic printing, and less commonly by gravure or offset printing. Screen printing is typically used only for special effects, such as raised structures, e.g. braille; or printing of security features. Digital printing methods, such as inkjet printing, are used here either as very small-scale operations or in combination with one of the conventional printing methods of personalized printing. Similar to the end use of newspapers, a central requirement for substrate wetting agents is the precise control of substrate wetting, in flexographic printing, and the surface of the printing blocks used to achieve a defect-free, precise printed image. This situation is similar to the recyclability of printing paper. High molecular weight substrate wetting agents with positive properties with respect to migration potential make a positive contribution to the improvement of quality and extend the possible uses of the substrate quality produced with recycled materials.

In the end use of gift wrapping paper, a wide range of very different paper qualities and in some cases film qualities are used. Ranging from substantially uncoated, white or brown substances of slightly calendered or structured quality, various coating and calendering qualities, to high quality metallized substrates and nonwovens. In the case of films, PET and OPP are typically printed, although other film types are possible. In this application, the challenge of substrate wetting agents is in particular the uniform and precise wetting of many different substrate qualities, since manufacturers usually produce only one color series, if at all possible, for logistics and storage reasons. Furthermore, in such design-driven end uses, the demands on the appearance and the corresponding exact printed image are very high. In addition, very high printing speeds (typically between 200 and 500 meters per minute) place high demands on substrate wettability. In particular, the printing methods employed are conventional gravure and flexographic printing. The use of screen printing is relatively rare and, if so, is generally only used for special effects, such as the printing of raised structures or very large effect pigments (e.g. nacres, glitters or flakes having a particle size of 60 μm or more). Digital printing methods such as inkjet are often used here for small-scale operations or to create sample collections. Furthermore, the low migration potential of the ingredients used is an important parameter in the case of being used for qualities close to the use of food products. Here, high molecular weight substrate wetting agents with their positive properties with respect to migration potential are positive factors.

In the end use of decorative papers (papers for consumer goods with natural or artificial decor, such as furniture, laminate floors, kitchen tops, etc.), absorbent papers with a slight to moderate coating are mainly used. Some of which are bulk-colored (bulk-colored). Furthermore, so-called prepregs are also printed, in which the decorative paper is pre-impregnated with a melamine resin solution. Printing is primarily by gravure printing, typically at machine speeds of 200 and 600 meters per minute. In this regard, the requirements described in other applications of high printing speed apply here as well. Flexographic printing has less of a role in decorative paper printing and is mainly used to produce simpler qualities such as upholstery for rear cabinet walls. However, similar to the end use already described, the requirements with respect to substrate wetting and printing plates also apply here. Digital printing methods such as inkjet are used here for small-scale operations or to create sample collections. At the same time, the importance of small-lot runs is increasing due to the trend of personalized design and the possibility of order-based production.

In particular, the mentioned substrate qualities, which on the one hand have a high absorption and on the other hand a melamine resin surface, require a substrate wetting agent with a specific action of clean printing in order firstly to avoid uncontrolled penetration of the ink into the printed material and secondly to reliably balance the uneven surface tension of the substrate. Furthermore, it is important that the substrate wetting agent does not lead to failures in downstream processing steps, in particular failures in the interlayer adhesion (substrate, decorative paper, outer layer).

In the end use of wallpaper, a wide range of very different substrate qualities are being used. Ranging from coated paper to PVC coated paper (also known in the industry as vinyl), to high quality uncoated and coated nonwoven fabric types. In the field of wallpaper, nonwoven fabric refers to paper quality typically having a synthetic fiber content (typically PE or PP) of 10% to 20%. The printing method used is likewise varied. Typically, manufacturers combine multiple printing methods with each other to achieve the desired effect of all design considerations in a single production line. Usually, flexographic or gravure printing is combined with rotary screen printing, roll coating and spread coating. In some cases, digital printing methods, such as inkjet or toner-based printing, may also be used for personalization and small batch runs.

The challenge of substrate wetting agents in such applications is in particular the uniform and precise wetting of many different substrate qualities using different printing methods, since producers in the conventional printing field usually produce only one color series, if at all possible. In addition, the demands on the appearance and the corresponding exact printed image are very high in this design-driven end use. In addition, very different printing speeds (typically between 40 and 300 meters per minute) place high demands on the wettability of the substrate. Furthermore, the various effect paints used (metallic effect pigments, nacre effect pigments, glitter, flakes, fluorescent pigments, conductive pigments, heat-sensitive pigments, etc.) put high demands on the wetting agent of the substrate, since the effects firstly require perfect wetting of the substrate and secondly require an optimum orientation of the effect pigments, which in most cases are in the form of thin layers (platlets).

In the end use of sanitary paper (napkins, kitchen paper, toilet paper, etc., specifically including wet wipes, cosmetic pads and the like), strongly absorbent paper is mainly used, with or without light calendering. However, in some cases, nonwoven qualities with different synthetic fiber contents (typically between 5% and 100%) are used. In individual end uses, one or more (typically 2-4) layers of substrate are used. In terms of the printing method, flexographic printing is mainly used. The machine speed is typically 150 meters per minute to 500 meters per minute. However, in some cases, embossing printing is used in which a colored adhesive is applied by a specific embossing roller, and printing (colour impression) is performed. This method is increasingly being used to produce toilet paper.

In particular, the substrate qualities mentioned with high absorption require that the substrate wetting agent has a specific action for clean printing in order firstly to avoid uncontrolled penetration of the ink into the printed material and secondly to reliably balance the uneven surface tension of the substrate. Furthermore, it is important that the substrate wetting agent ensures good wetting of the fibers in order to achieve good adhesion of the applied color film and thus to meet the prerequisites for achieving bleed fastness according to DIN EN 646, which are requirements for these end uses. Since the end use is primarily near the food or in the cosmetics, the requirements for the substrate wetting agent are of course correspondingly higher in terms of low mobility.

In the end use of the label, a variety of lightly or highly coated paper qualities are used. In some cases, the quality of the metallization is also used. Furthermore, a variety of different foil qualities are also used. However, in the case of products from the low cost sector, lightly calendered paper without a coating is also used. Printing is often achieved by flexographic, gravure or offset printing. Screen printing is typically used only for special effects, such as raised structures, e.g. braille; or printing of security features. Digital printing methods, such as inkjet printing, are used here either for small-scale operations or in combination with one of the conventional printing methods for personalized printing. Similar to the end use of form printing, a central requirement for substrate wetting agents is precise control of substrate wetting and, in flexographic printing and on the surface of the printing blocks used, to achieve a defect-free, precise printed image. This situation is similar to the recyclability of printing paper. High molecular weight substrate wetting agents with positive properties with respect to migration potential make a positive contribution to the improvement of quality and extend the possible uses of the substrate quality produced with recycled materials.

In the end use of aseptic beverage packaging and similar paperboard packaging, primed paper and card qualities are used. The requirements for printability and the substrate wetting agent used are similar to those described for the end use of corrugated board.

The printing properties are similar to those of coated papers used for the production of corrugated board. By virtue of the high regulatory requirements in such end use, the requirements with respect to defined efficacy and minimal migration potential are particularly high in the case of paints and varnishes for these packaging materials. This necessitates the use of substrate wetting agents optimized in this respect.

In the end use of packaging films, a variety of film qualities are used. Ranging from PE, PP, OPP, BOPP, PET, PEN (polyethylene naphthalate, e.g. polyethylene naphthalate)

Polyesters (e.g. of the formulae

Or

) Cellulose hydrate film

PVC (polyvinyl chloride) to "biofilms", such as PLA (polylactic acid). This list is illustrative only. All other possible film substrates are expressly included. The same applies in the case of the films mentioned hereinafter, which have various protective or functional or effect coatings. In some cases, these films are also used, which have been provided with various protective coatings (PVDC, EVOH, SiO)_x、AlO_xEtc.), functional coatings (e.g., nanoparticles for improving scratch resistance and other mechanical properties, e.g.

Nanoresins) or metallization.

Printing is typically achieved by flexographic or gravure printing. Screen printing is typically used only for special effects, such as raised structures, e.g. braille; or printing of security features. Digital printing methods, such as inkjet printing, are used here either for small-scale operations or in combination with one of the conventional printing methods of personalized printing. Another area where ink jet printing is used is in printing bar codes and product information, such as shelf life/best use date. In the industry, this part is also referred to as coding and marking. Similar to other end uses for non-absorbent substrates that have been described, a central requirement for substrate wetting agents is precise control of substrate wetting and, in flexographic printing, and the surface of the printing block used, to achieve a defect-free, accurately printed image. This is similar to the recyclability of printed films. High molecular weight substrate wetting agents with positive properties with respect to migration potential make a positive contribution to the improvement of quality and extend the possible uses of the substrate quality produced with recycled materials.

The present invention also provides a composition comprising:

a) at least one compound of formula (I) or (II),

b) optionally one or more pigments and fillers,

c) at least one kind of adhesive agent is used,

d) optionally one or more waxes, which are present,

e) (ii) optionally at least one solvent present,

f) optionally one or more film-forming auxiliaries (coalescents),

g) optionally one or more rheological additives,

h) optionally one or more anti-foaming agents,

i) optionally one or more neutralizing agents,

j) optionally other components (e.g., retarders, slip additives, etc.),

preferred compositions according to the invention comprise:

a) at least one compound of formula (I) or (II),

b) optionally one or more pigments and fillers,

c) at least one kind of adhesive agent is used,

d) optionally one or more waxes, which are present,

e) at least one kind of solvent is used as the solvent,

f) optionally one or more film-forming auxiliaries (coalescents),

g) optionally one or more rheological additives,

h) optionally one or more anti-foaming agents,

i) optionally one or more neutralizing agents,

j) optionally other components (e.g., retarders, slip additives, etc.),

particularly preferred compositions according to the invention comprise:

a) at least one compound of formula (I) or (II),

b) one or more pigments and fillers, preferably selected from pigment white 6 (rutile or anatase modification of titanium dioxide), pigment black 7 (carbon black), pigment blue 15:3 or pigment blue 15:4 (phthalocyanine pigments), pigment red 57:1 (lake BONA pigments (BONA ═ β -naphthoic acid)), pigment yellow 12, pigment yellow 13 (benzidine yellow and benzidine orange pigments), pigment violet 23 (dioxazine pigments) and/or pigment green 7 (phthalocyanine pigments),

c) at least one kind of adhesive agent is used,

d) optionally one or more waxes, which are present,

e) (ii) optionally at least one solvent present,

f) optionally one or more film-forming auxiliaries (coalescents),

g) optionally one or more rheological additives,

h) optionally one or more anti-foaming agents,

i) optionally one or more neutralizing agents,

j) optionally other components (e.g., retarders, slip additives, etc.),

particularly preferred compositions according to the invention comprise:

a) at least one compound of formula (I) or (II),

b) optionally one or more pigments and fillers,

c) at least one kind of adhesive agent is used,

d) optionally one or more waxes, which are present,

e) (ii) optionally at least one solvent present,

f) optionally one or more film-forming auxiliaries (coalescents),

g) optionally one or more rheological additives,

h) one or more defoaming agents in combination with one or more surfactants,

i) optionally one or more neutralizing agents,

j) optionally other components (e.g., retarders, slip additives, etc.),

particularly preferred compositions according to the invention comprise:

a) at least one compound of formula (I) or (II),

c) at least one kind of adhesive agent is used,

d) optionally one or more waxes, which are present,

e) at least one solvent, preferably at least one solvent selected from water, ethanol, isopropanol and/or ethyl acetate,

f) optionally one or more film-forming auxiliaries (coalescents),

g) optionally one or more rheological additives,

h) one or more defoaming agents in combination with one or more surfactants,

i) optionally one or more neutralizing agents,

j) optionally other components (e.g., retarders, slip additives, etc.),

particularly suitable for use as printing colours, printing inks or printing varnishes and other colours, varnishes, inks, colour formulations and coatings, which are applied by analogue or digital coating methods to the above-mentioned substrates and fields of use.

Pigments and fillers (b component):

in the following list, the pigment types are described using the international standard color index.

These include in particular organic pigments:

monoazo yellow and monoazo orange pigments (e.g. pigment yellow 1, pigment yellow 74, pigment yellow 111 or pigment orange 1), benzidine yellow and benzidine orange pigments (e.g. pigment yellow 12, pigment yellow 13, pigment yellow 14, pigment orange 16), bisacetoacetarylide pigments (e.g. pigment yellow 16, pigment yellow 155), bisazopyrazolinone pigments (e.g. pigment orange 13, pigment orange 34), β -naphthol pigments (e.g. pigment orange 5, pigment red 1), naphthol AS pigments (e.g. pigment red 2, pigment red 170, pigment red 184), laked β -naphthol pigments (e.g. pigment red 49:2, pigment red 53:1), laked BONA pigments (e.g. pigment red 48:3, pigment red 57:1), laked naphthol AS pigments (e.g. pigment red 151, pigment red 247), pigment red 247, and mixtures thereof, Laked naphthalene sulfonic acid pigments (e.g., pigment yellow 104, pigment Red 60:1), benzimidazole pigments (e.g., pigment yellow 151, pigment yellow 181, pigment Red 208, pigment Violet 32), diazo condensation pigments (e.g., pigment yellow 93, pigment Red 166, pigment Red 242), metal complex pigments (e.g., pigment yellow 150, pigment Red 257), isoindolinones and isoindoline pigments (e.g., pigment yellow 110, pigment yellow 185), phthalocyanine pigments (e.g., pigment blue 15:3, pigment blue 15:4, pigment blue 16, pigment Green 7), quinacridone pigments (e.g., pigment Violet 19, pigment Red 122, pigment Red 202, pigment Red 282), perylene and perinone pigments (e.g., pigment Red 123, pigment Red 178, pigment Black 31, pigment Black 32, pigment orange 43, pigment Red 194), thioindigo pigments (e.g., pigment Red 88, pigment Red 181), aminoanthraquinone pigments (e.g., pigment yellow 147, pigment Red, Pigment 89, pigment red 177, pigment blue 60, pigment violet 31), dioxazine pigments (for example: pigment violet 23, pigment violet 37), triarylcarbonium (triarylcarbonium) pigments (for example: pigment blue 56, pigment blue 61, pigment violet 3, pigment violet 27, pigment blue 62, pigment red 81:1, pigment red 81:3), quinophthalone pigments (for example: pigment yellow 138), Diketopyrrolopyrrole (DPP) pigments (e.g.: pigment red 254, pigment red 255), aluminum lake pigment (for example: pigment red 172, pigment blue 24:1, pigment blue 63), other organic pigments (e.g.: pigment yellow 148, pigment yellow 182, pigment orange 64, pigment red 252, pigment brown 22, pigment black 1).

Furthermore, these include, in particular, inorganic pigments:

iron oxide pigments (e.g., pigment yellow 42, pigment red 101, pigment black 11), chromium oxide pigments (e.g., pigment green 17), ultramarine pigments (e.g., pigment blue 29, pigment violet 15, pigment red 259); composite inorganic color pigments (rutile type pigments: e.g., pigment brown 24, pigment yellow 53, pigment yellow 164, or spinel pigments: e.g., pigment blue 28, pigment blue 36, pigment green 50, pigment yellow 119, pigment brown 29, pigment black 22, pigment black 27, pigment black 28); cadmium pigments (e.g., pigment yellow 35, pigment yellow 37, pigment orange 20, pigment red 108); bismuth vanadate pigments (e.g., pigment yellow 184); cerium sulfide pigments (e.g., pigment orange 75, pigment red 265), chromate pigments (e.g., pigment yellow 34), white pigments: (e.g., pigment white 4 (zinc white), pigment white 5 (lithopone consisting of barium sulfate and zinc sulfide), pigment white 6 (rutile or anatase modification of titanium dioxide), pigment white 7 (zinc sulfide), pigment white 14 (calcium carbonate), pigment white 21 and 22 (white);

black pigments (e.g., pigment Black 1 (nigrosine) and pigment Black 7 (carbon black)).

Furthermore, these include, inter alia, effect pigments:

nacre pigments (e.g. from Merck)

Pigments), glitter (e.g., glitter products available from RJA Plastics GmbH), flakes (e.g., aluminum products available from RJA Plastics GmbH), luminescent pigments (e.g., Lumilux products available from Honeywell), magnetic pigments (e.g., iron oxide products available from Cathay Industries), anti-corrosive pigments (e.g., zinc phosphate, aluminum phosphate, etc.), metal effect pigments (e.g., pigments based on aluminum, copper, gold bronze (copper-zinc alloy), zinc and other metals, e.g., made by Carl Schlenk AG or Silberline Manufacturing co.

The following pigments are particularly preferred for use in many end uses:

pigment white 6 (rutile or anatase modification of titanium dioxide), pigment black 7 (carbon black), pigment blue 15:3 or pigment blue 15:4,

(phthalocyanine pigment), pigment Red 57:1 (lake BONA pigment (BONA ═ beta-naphthoic acid)), pigment yellow 12 or pigment yellow 13,

(benzidine yellow and benzidine orange pigments), pigment violet 23,

(dioxazine pigments), pigment green 7 (phthalocyanine pigments).

Preferred fillers are: such as chalk (calcium carbonate), magnesium (magnesium carbonate), barium sulfate, and the like. The term "filler" also includes organic and inorganic matting agents (e.g. available from Evonik Industries AG)

And

product) and all other fillers and matting agents that may be used in the applications described herein.

Binder (component c)):

the following are preferably available: acrylic adhesives (e.g. under the trade mark by Indulor AG

Prepared or sold by Evonik Industries AG under the trademark Evonik

Prepared), styrene acrylate adhesive (e.g., by BASF SE under the trademark mack (r))

Prepared or sold under the trademark INDULOR AG

Prepared), polyester binder (e.g., by Evonik Industries AG under the trademark Evonik @)

Or

Prepared), polyol resins (e.g. by Evonik Industries AG under the trade mark

Prepared), maleate and fumarate binders (e.g. by Robert Kraemer under the trade mark

Prepared), binders based on natural raw materials (for example based on sugar, starch, cellulose, casein, soy protein and derivatives thereof and other types based on natural raw materials), polyvinyl alcohol binders (trademarks by Indulor AG)

Prepared), as well as all other adhesives that may be used in the applications described herein. Here, some adhesives supplied (e.g. Induprint SE 900) may be used, while others are used only after neutralization (e.g. Indurez SR 10) or other processing steps (e.g. casein).

Waxes and additives with similar effects (component d)):

preferred waxes that may be used include Polyethylene (PE) wax, polypropylene (PP) wax, polytetrafluoroethylene wax (PTFE), Fischer-Tropsch wax, amide wax, paraffin wax, carnauba wax, and all other waxes and wax-like substances that may be used for the applications described herein.

Solvent (component e)):

preferably solvents that can be used are water or organic solvents (e.g. ethanol, isopropanol, butanol, methoxypropanol, ethoxypropanol, ethyl acetate, methyl ethyl ketone), alone or in combination with each other, and any desired combination of all other solvents that can be used for the applications described herein. Particular preference is given to using water, ethanol, isopropanol and ethyl acetate.

Film-forming auxiliaries (coalescents) (component f)):

film-forming auxiliaries which can preferably be used are: such as glycols, e.g., Dowanol DPnB, and alcohols, e.g., ethanol, as well as all other coalescents that may be used in the applications described herein.

Rheological additive (component g)):

preferred rheological additives that may be used are organic rheological additives (e.g. acrylate thickeners (e.g. from Indulor AG and so on)

Prepared under the name T256, or by BASF SE

Name of AS 1125 SA (original)

D) Prepared) or polyurethane thickeners (e.g. by Evonik Industries AG under the trade mark

Or from Munzing Chemie in the order of

Pur name) and inorganic rheological additives (e.g., manufactured by Evonik Industries AG under the trademark Evonik

Or by Elementis to

Prepared)

Antifoam (component h)):

preferred defoamers which can be used are: such as organic-based defoaming additives (e.g., products made by Evonik Industries AG)

Foamex 833 or

Foamex 831) or silicone-based antifoam additives (e.g. products from Evonik Industries AG, e.g.

Foamex N or

Foamex 3062) and all other antifoam substances that may be used for the applications described herein.

Neutralizer (component i)):

preferred neutralizing agents that can be used are amines (e.g., ammonia, DEMA, TEA, AMP, etc.), inorganic neutralizing agents (e.g., sodium hydroxide solution, potassium hydroxide solution, etc.), and all other neutralizing agents that can be used for the applications described herein.

Other components (component j)):

these include:

retarders for adjusting the drying rate (e.g. glycerol, propane-1, 2-diol, glycols such as polyethylene glycol (e.g. PEG 200 or PEG 400))

Slip additives for adjusting the surface smoothness (e.g. available from Evonik Industries AG)

Glide 482)

Preservatives for reducing corrosion of paint or varnish-directing application devices, storage or transport containers or metering systems (e.g. from Raschig GmbH)

99)。

Markings, for example for marking cut lines, as a security feature or for checking the quality of the application (in particular in the case of uncolored systems) (for example, to

Sold under the name of Blankophor GmbH&Product of Co.KG)

Microencapsulated active ingredients, e.g. from Follmann GmbH&Microencapsulated fragrance FOLCO of Co KG

Plasticizers for the permanent elastification of applied paint or clear coats (e.g. from Evonik Industries AG)

CH)

Adhesion promoters for difficult substrates (e.g. from Evonik Industries for improving adhesion on substrates such as glass or aluminium)

900)

Conductive additives for modifying the surface conductivity of the applied paint or clear coat layer (e.g. available from Evonik Industries AG)

240)

Specific surface effect additives (available from Evonik Industries AG for achieving the hammer effect of paints and varnishes)

Hammer 501)

Hydrophobic agents for obtaining the hydrophobicity of the applied paint or clear coat layer (e.g. available from Evonik Industries AG)

Phobe 1650)

And preferably all other components that can be advantageously used in the applications described herein.

Preferred compositions of the invention comprise:

a) from 0.1% to 20% by weight, preferably from 0.5% to 1.5% by weight, of at least one compound of the formula (I) or (II),

b)0.0 to 75% by weight, preferably 2 to 50% by weight, more preferably 4 to 25% by weight, of at least one pigment, preferably at least one pigment selected from pigment white 6 (rutile or anatase modification of titanium dioxide), pigment black 7 (carbon black), pigment blue 15:3 or pigment blue 15:4 (phthalocyanine pigment), pigment red 57:1 (lake BONA pigment (BONA. beta. -naphthoic acid)), pigment yellow 12, pigment yellow 13 (benzidine yellow and benzidine orange pigment), pigment violet 23 (dioxazine pigment) and/or pigment green 7 (phthalocyanine pigment),

c) from 0.5% to 80% by weight, preferably from 2% to 40% by weight, more preferably from 7% to 30% by weight, of at least one binder,

d) from 0.0% to 10% by weight, preferably from 0.5% to 5% by weight, more preferably from 1% to 2% by weight, of at least one wax,

e) from 0.5% to 80% by weight, preferably from 10% to 60% by weight, more preferably from 20% to 50% by weight, of at least one solvent, preferably at least one solvent selected from water, ethanol, isopropanol and/or ethyl acetate,

f) from 0.5% to 70% by weight, preferably from 1% to 10% by weight, more preferably from 1% to 3% by weight, of at least one film-forming auxiliary,

g) 0.0% to 10% by weight, preferably 0.2% to 5% by weight, more preferably 0.5% to 2% by weight, of at least one rheological additive,

h) 0.0% to 5% by weight, preferably 0.05% to 2% by weight, more preferably 0.2% to 1% by weight, of at least one defoaming agent,

i) from 0.0% to 15% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.2% to 5% by weight, of at least one neutralizing agent,

j) from 0.0% to 25% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.2% to 5% by weight, of at least one of the components listed under j,

wherein the sum of all components taken together is 100% by weight and all weight percents are based on the total weight of the composition.

The following examples illustrate the invention by way of example and are not intended to limit the invention to the embodiments specified in the examples, the scope of applicability of the invention being apparent from the description and claims taken in their entirety.

Example (b):

the test method comprises the following steps:

the parameters or measurements are preferably determined using the methods described below. In particular, these methods are used in embodiments of the present intellectual property.

In the context of the present invention, the weight and number average molecular weights of the eugenol-based polyethers prepared are determined by Gel Permeation Chromatography (GPC) calibrated with polypropylene glycol standards, and those of the eugenol polyether-containing polysiloxanes calibrated with polystyrene standards. GPC was performed at a temperature of 30 ℃ and a flow rate (mobile phase THF) of 1mL/min using an Agilent 1100 instrument equipped with an RI detector and SDV

A column combination, the column consisting of a 0.8 × 5cm pre-packed column and two 0.8 × 30cm main columns. The sample concentration was 10g/L and the injection volume was 20. mu.L.

NMR spectra were measured on a 5mm QMP head using a Bruker 400MHz spectrometer. Quantitative NMR spectra were measured in the presence of a suitable promoter. The sample to be analyzed is dissolved in a suitable deuterated solvent (methanol, chloroform) and transferred to a 5mm or, if appropriate, 10mm NMR tube.

Wet chemical analysis was performed according to international standard methods: iodine value (IN; DGF C-V11 (53), acid value (AN; DGF C-V2), and OH number (ASTM D4274C).

Dynamic surface tension was measured with a SITA f10 bubble pressure tensiometer as follows: a 0.5% solution of the substance to be analyzed was prepared in deionized water. After being left for 24 hours, the samples were analyzed in the frequency range from 10 to 1 Hz. Before each series of measurements, the tensiometer was calibrated with demineralized water.

The static surface tension is measured with a Kruss K100 tensiometer according to DIN EN 14370.

Example 1: synthesis of eugenol-based polyethers (invention):

first, 351g of eugenol were charged to a 5 liter autoclave and 100ppm (based on the total mixture) of zinc hexacyanocobaltate double metal cyanide catalyst was added. The reactor was inerted by injecting nitrogen to 3bar and subsequently depressurising to standard pressure. This operation was repeated two more times. The contents of the reactor were heated to 100 ℃ while stirring and a vacuum was applied to about 20mbar to remove volatile components. After 30 minutes, the temperature is raised toAt 130 ℃, 100g of propylene oxide were metered into the evacuated reactor to activate the catalyst. First, the internal pressure rises to about 0.8 bar. The pressure began to drop slowly and had dropped to-0.1 bar after about 7 minutes. Then, a further 50g of PO were metered in and the pressure was again increased to 0.8 bar. After 12 minutes, the pressure had dropped to-0.1 bar and a further 50g of PO were metered in. Once the pressure had dropped to 0bar, slow continuous metering of PO was started. After a total of 210g of PO was added, the pressure dropped abruptly to-0.9 bar, which was used to indicate the actual start of the reaction. Then, over the course of about 10 minutes, 38g of propylene oxide were metered in continuously. After which the reaction was carried out for another one hour. A mixture of 1,110g of EO and 1,290g of PO was then metered in continuously, so that the temperature remained constant. After a further half hour of reaction, pressure (P) is applied<20mbar) to remove the residues of unconverted alkylene oxide. Then, 500ppm of ANOX 20AM was added with stirring over 15 minutes. A colorless to pale yellow product is obtained having AN OH number of 40.2mg KOH/g and AN AN of 0.1mg KOH/g. The molecular weight according to OH number was 1,395 g/mol. According to GPC, M_w＝1,394g/mol，M_n1,316g/mol, and PDI is 1.06.

Example 2: synthesis of eugenol-based polyethers (invention):

first, 164.2g of eugenol was charged to a 5 liter autoclave and 100ppm (based on the total mixture) of zinc hexacyanocobaltate double metal cyanide catalyst was added. The reactor was inerted by injecting nitrogen to 3bar and subsequently depressurising to standard pressure. This operation was repeated two more times. The contents of the reactor were heated to 100 ℃ while stirring and a vacuum was applied to about 20mbar to remove volatile components. After 30 minutes, the temperature was raised to 130 ℃ and 70g of propylene oxide were metered into the evacuated reactor to activate the catalyst. First, the internal pressure rises to about 0.8 bar. The pressure began to drop slowly and had dropped to-0.4 bar after about 30 minutes. Then the slow, continuous addition of propylene oxide was started. After a further 56g of PO were added, the pressure rose to 0.7bar and then suddenly dropped to-0.8 bar after a total of 200g of PO had been added, and this sudden drop in pressure was used to indicate the actual start of the reaction.1,673g of propylene oxide were then metered in continuously, so that the temperature was kept constant. After a further half hour of reaction, pressure (P) is applied<20mbar) to remove the residues of unconverted alkylene oxide. Then, 500ppm of ANOX 20AM was added with stirring over 15 minutes. A colorless to pale yellow product is obtained having AN OH number of 26.8mg KOH/g and AN AN of 0.1mg KOH/g. The molecular weight is 2,093g/mol, based on the OH number. According to GPC, M_w＝1,957g/mol，M_n1,830g/mol, and PDI is 1.07.

Example 3: synthesis based on eugenol polyether (invention):

first, 544g of eugenol was charged to a 5 liter autoclave and 200ppm (based on the total mixture) of zinc hexacyanocobaltate double metal cyanide catalyst was added. The reactor was inerted by injecting nitrogen to 3bar and subsequently depressurising to standard pressure. This operation was repeated two more times. The contents of the reactor were heated to 80 ℃ while stirring and a vacuum was applied to about 20mbar to remove volatile components. After 30 minutes, the temperature was raised to 140 ℃ and 80g of propylene oxide were metered into the evacuated reactor to activate the catalyst. First, the internal pressure rises to about 0.6 bar. The pressure began to drop slowly and had dropped to-0.2 bar after about 10 minutes. Then, 74g of PO were metered in again, which slowly reduced the pressure to-0.8 bar over a period of 60 minutes. Then, the metering of a mixture of 612g of ethylene oxide and 691g of propylene oxide was started. 110g of an EO/PO mixture are metered in over 30 minutes, which raises the pressure in the reactor to 0.5 bar. Then, an additional 54g of the mixture was added over 15 minutes. The pressure rose to 1.5bar and then dropped abruptly to-0.5 bar, which was used to indicate the actual start of the reaction. The remaining alkylene oxide mixture (1,139g) was then metered in continuously over the course of 40 minutes. After a further half hour of reaction, pressure (P) is applied<20mbar) to remove the residues of unconverted alkylene oxide. Then, 500ppm of ANOX 20AM was added with stirring over 15 minutes. A colorless to pale yellow product is obtained having AN OH number of 81.8mg KOH/g and AN AN of 0.1mg KOH/g. The molecular weight is 685g/mol, based on the OH number. According to GPC, M_w＝640g/mol，M_n583g/mol, and PDI is 1.10.

Example 4: synthesis based on eugenol polyether (invention):

first, 503g of eugenol were charged to a 5 liter autoclave and 100ppm (based on the total mixture) of zinc hexacyanocobaltate double metal cyanide catalyst was added. The reactor was inerted by injecting nitrogen to 3bar and subsequently depressurising to standard pressure. This operation was repeated two more times. The contents of the reactor were heated to 120 ℃ while stirring and a vacuum was applied to about 20mbar to remove volatile components. After 30 minutes, the temperature was raised to 130 ℃ and 70g of propylene oxide were metered into the evacuated reactor to activate the catalyst. First, the internal pressure rises to about 0.5 bar. The pressure began to drop slowly and had dropped to-0.9 bar after about 20 minutes. Then, 196g of PO were slowly metered in over a period of 40 minutes, which brought the pressure to 0.5 bar. After 30 minutes of post-reaction, the pressure had dropped to-0.4 bar and the metering of a mixture of 1,078g EO and 1,154g PO was started. 60g of the EO/PO mixture were metered in over 30 minutes, which caused the pressure in the reactor to initially rise to a slight positive pressure and then to suddenly drop to-0.9 bar, which was used to indicate the actual start of the reaction. The remaining alkylene oxide mixture (2,172g) was then metered in continuously over 75 minutes. After a further half hour of reaction, pressure (P) is applied<20mbar) to remove the residues of unconverted alkylene oxide. Then, 500ppm of ANOX 20AM was added with stirring over 15 minutes. A colorless to pale yellow product is obtained having AN OH number of 51.6mg KOH/g and AN AN of 0.1mg KOH/g. The molecular weight is 1,087g/mol, based on the OH number. According to GPC, M_w＝1,012g/mol，M_n945g/mol, and PDI is 1.07.

Example 5: acetylation of eugenol-based polyethers from example 1 (invention)

A 2 l three-necked flask equipped with a dropping funnel and a reflux condenser was initially charged with eugenol-based polyether from example 1 and a catalytic amount of concentrated hydrochloric acid under protective gas, and the resulting mixture was heated. Then, acetic anhydride was slowly added. Once the addition was complete, the mixture was stirred for an additional 4 hours. Then, any residual acid was distilled off to give a colorless to pale yellow product having 0.1OH number of mg KOH/g and AN of 0.1mg KOH/g. Within the range of analytical measurement uncertainties, the OH value indicates quantitative acetylation of the terminal OH groups of the polyether. GPC remained unchanged compared to the polyether from example 1 over the range of measurement uncertainty for the two independent measurements. According to GPC, M_w＝1,424g/mol，M_n1,316g/mol, and PDI is 1.08.

Example 6: methylation of eugenol-based polyethers (invention):

a 2 l three-necked flask equipped with a dropping funnel and a reflux condenser was initially charged with eugenol-based polyether from example 1 together with excess sodium methoxide under protective gas and the resulting mixture was heated. Then, methanol was distilled off under reduced pressure and methyl chloride was introduced. Once the addition was complete, the mixture was stirred for an additional 4 hours. The product was neutralized with dilute phosphoric acid. Water was removed by distillation under the reduced pressure, and the resulting salt was filtered off, and a pale yellow product was obtained, which corresponds to the isoeugenol polyether, having AN OH number of 1.0mg KOH/g and AN of 0.1mg KOH/g. In the range of analytical measurement uncertainties, the OH value indicates a nearly quantitative level of terminal OH groups of 97.5% polyethers. GPC remained unchanged compared to the polyether from example 1 over the range of measurement uncertainty for the two independent measurements. According to GPC, M_w＝1,416g/mol，M_n1,324g/mol, and PDI is 1.07.

Example 7: phosphorylation of eugenol-based polyethers (invention):

first, 1,395g of eugenol-based polyether from example 1 was charged to the reactor, about 50mL of toluene was added, and the mixture was heated to 110 ℃. By the application of reduced pressure, all volatile constituents, in particular any water present in the product, are removed from the reaction space by distillation. After degassing with nitrogen, the mixture was heated to 80 ℃ and 85g of liquid polyphosphoric acid (0.25mol P) were added₄O₁₀(ii) a The manufacturer: merck; in an amount of P₄O₁₀And (3) calculating: about 85%). After 2 hours, the reaction was complete. In that¹In the H NMR spectrum, no more aliphatic hydroxyl groups are detectable.

Example 8 a: synthesis of polyethers based on isoeugenol from eugenol by base catalysis (invention):

the starting weights for the syntheses correspond to those from example 1. First, eugenol was charged to a 5 liter autoclave along with 8 mole percent potassium methoxide. The reactor was inerted by injecting nitrogen to 3bar and subsequently depressurising to standard pressure. This operation was repeated two more times. While stirring, the contents of the reactor were heated to 100 ℃ and a vacuum was applied to about 20mbar to remove methanol from the catalytic step. Then 248g of PO were added at a temperature of 115 ℃ so that the pressure in the reactor did not rise above 2 bar. Then, a mixture of 1,110g EO and 1,290g PO was metered in continuously so that the temperature was kept constant and the pressure did not rise above 2 bar. After both addition stages, the time at which the pressure no longer drops is waited for, which is taken as an indication of a substantially quantitative conversion of the alkylene oxide. To complete the alkylene oxide conversion, the reaction was carried out for one more hour after the first PO stage and after the random EO/PO stage. Finally, by applying pressure (P)<20mbar) to remove the residues of unconverted alkylene oxide. The polyether was then neutralized with dilute phosphoric acid and stabilized with 500ppm ANOX 20 AM. Then, water was removed by distillation under reduced pressure at 120 ℃ and the precipitated salt was removed by filtration. A colorless to pale yellow product having AN OH number of 41.3mg KOH/g and AN AN of 0.2mg KOH/g was obtained. The molecular weight was 1,358g/mol in terms of OH number. According to GPC, M_w＝1,370g/mol，M_n1,248g/mol, and PDI is 1.10.

Example 8 b: synthesis of polyethers based on isoeugenol from isoeugenol by base catalysis (invention):

the synthesis of example 8a (1:1) was carried out, except that, instead of eugenol, the same amount of isoeugenol was used. This gave a pale yellow isoeugenol polyether having AN OH number of 39.8mg KOH/g and AN AN of 0.3mg KOH/g. The molecular weight was 1,410g/mol in terms of OH number. According to GPC, M_w＝1,393g/mol，M_n1,675g/mol and PDI is 1.27.

Example 9: preparation of polyether siloxanes with eugenol-based polyethers (invention):

is provided with a thermometer and is cooled by refluxA500 mL three-necked flask with a condenser and precision glass stirrer was charged with 79.0g of a mixture of the formula [ Me₂SiHO_1/2]₂[Me₂SiO_2/2]₃₇[MeSiHO_2/2]₃With 171g of eugenol-based polyether from example 4. The mixture was stirred and heated to 90 ℃. The reaction mixture was then mixed with a solution of 0.17g Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for two hours. A yellowish clear single-phase liquid was obtained.

Example 10: preparation of polyether siloxanes with eugenol-based polyethers (invention):

44.3g of a mixture of the general formula [ Me ] were mixed in a 500mL three-necked flask equipped with a thermometer, reflux condenser and precision glass stirrer₃SiO_1/2]₂[Me₂SiO_2/2]₁₃[MeSiHO_2/2]₅With 205.7g of eugenol-based polyether from example 4. The mixture was stirred and heated to 90 ℃. The reaction mixture was then mixed with a solution of 0.17g Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for two hours. A yellowish clear single-phase liquid was obtained.

Example 11: polyether siloxanes were prepared with polyethers not based on eugenol as well as with polyethers based on eugenol (invention):

40.0g of a mixture of the general formula [ Me ] was mixed in a 500mL three-necked flask equipped with a thermometer, reflux condenser and precision glass stirrer₃SiO_1/2]₂[Me₂SiO_2/2]₁₃[MeSiHO_2/2]₅SiH-functional siloxanes with 94.8g of eugenol-based polyether from example 4 and 132.7g of a polyether of the formula CH₂＝CHCH₂O-(CH₂CH₂O)₁₃(CH₂CH(CH₃)O)₁₃Me. The mixture was stirred and heated to 90 ℃. The reaction mixture was then mixed with a solution of 0.18g Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed.The mixture was stirred for two hours. A yellowish clear single-phase liquid was obtained.

Example 12: preparation of polyether siloxanes with eugenol-based polyethers (invention):

112.0g of a mixture of the general formula [ Me ] were mixed in a 500mL three-necked flask equipped with a thermometer, reflux condenser and precision glass stirrer₂SiHO_1/2]₂[Me₂SiO_2/2]₂₈With 138.0g of eugenol-based polyether from example 4. The mixture was stirred and heated to 90 ℃. The reaction mixture was then mixed with a solution of 0.17g Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for two hours. A yellowish clear single-phase liquid was obtained.

Example 13: preparation of polyether siloxanes with eugenol-based polyethers (invention):

in a 500mL three necked flask equipped with a thermometer, reflux condenser and precision glass stirrer was mixed 32.6 formula [ Me₃SiO_1/2]₂[MeSiHO_2/2]₁With 267g of eugenol-based polyether from example 1. The mixture was stirred and heated to 90 ℃. The reaction mixture was then mixed with a solution of 0.2g Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for 5 hours. A yellowish clear single-phase liquid was obtained.

Example 14: preparation of polyether siloxanes with eugenol-based polyethers (invention):

in a 500mL three necked flask equipped with a thermometer, reflux condenser and precision glass stirrer was mixed 50.0 formula [ Me₃SiO_1/2]₂[Me₂SiO_2/2]_1.75[MeSiHO_2/2]_1.25With 257g of eugenol-based polyether from example 1. The mixture was stirred and heated to 90 ℃. The reaction mixture was then mixed with a solution of 0.2g Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for 5 hours. To obtainTo a yellowish clear single-phase liquid.

Example 15: preparation of polyether siloxanes with polyethers not based on eugenol and with eugenol (invention):

150g of a mixture of the general formula [ Me ] in a 500mL three-necked flask equipped with a thermometer, reflux condenser and precision glass stirrer₃SiO_1/2]₂[Me₂SiO_2/2]₁₁₃[MeSiHO_2/2]₅SiH-functional siloxanes with 45.9g of eugenol-based polyether from example 4 and 55.1g of a polyether of the formula CH₂＝CHCH₂O-(CH₂CH₂O)₁₃(CH₂CH(CH₃)O)₂H, a polyether of H. The mixture was stirred and heated to 90 ℃. The reaction mixture was then mixed with a solution of 0.15g Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for two hours. A yellowish slightly turbid liquid was obtained.

Example 16: preparation of polyether siloxanes with eugenol-based polyethers and dodecenes (invention):

first, 164g of a compound of the formula Me₃SiO[SiMe₂O]₇₀[SiHMeO]₂₀SiMe₃The SiH-functional siloxane of (1L) was charged to a three-necked flask. The mixture was heated to 80 ℃ and mixed with 6mg of Pt (platinum) in the form of Karstedt catalyst. Then, 44g of 1-dodecene was slowly added dropwise. 424g of the polyether from example 4 were then metered in slowly. The reaction mixture was stirred at 80 ℃ for a further 2 hours. A clear and homogeneous alkyl-and polyether-modified siloxane is obtained.

Example 17: primary screening:

for preliminary screening, a variety of synthetic humectants were incorporated into four simplified model inks (TS 162/03 to TS 162/06) at 0.5% ratio to the reference product.

Formula of clear lacquer base TS 128/011

Formula of clear lacquer base TS 128/003

Cyan pigment base (pigment blue 15:3) formulation

The formulation is adjusted to a viscosity of 22-25 "(DIN 4 cup at 20 ℃) by adding water.

The test formulations were applied to the siliconized film with a bar (12 μm). The wettability was assessed visually with reference to the scale detailed below.

Example 18: evaluation of the properties in the end use of corrugated cardboard:

to test the preparation of the formulations, 10% of pigment base and 90% of extender are mixed and adjusted to a viscosity of 22-25 "(DIN 4 cup at 20 ℃) by adding water. The test formulations were applied by means of a laboratory contact pressure applicator (Erichsen Printing Proofer or

Labratester) or narrow format flexo presses (windmeyer and Hoelscher) to a variety of corrugated cardboard substrates.

Formula of clear lacquer base TS 128/003

To prepare the clear binder, the liquid components are first charged into a stainless steel container and heated to 70 ℃ by means of a hot plate with stirring (at a speed of 800rpm in a dissolver). Then, the solid resin was added to the mixture, which was then stirred with a dissolver at 800rpm until the solid resin had been sufficiently neutralized. The pH is checked periodically by means of a calibrated pH meter and, if necessary, more neutralizing agent is metered in. The target pH was 8.2-8.8.

Cyan pigment based formulations

Cyan (pigment blue 15:3)

To prepare the pigment base, the liquid components were first charged into a wide-mouth glass bottle and stirred with a dissolver at a speed of 800rpm for 5 minutes. The pigment was then added to the mixture, followed by pre-dispersion with a dissolver at 3,000rpm for 20 minutes. Then, an equal amount of glass beads (diameter 2-2.5mm) was added to the mixture and the bottle was sealed and shaken in a Lau disperser (shaker) for 3 hours with 20% cooling. Finally, the glass beads were filtered off and the pigment base was transferred to a new jar.

Bulking agents

To prepare the extender, first, water was added to a stainless steel container and the other components were added while stirring with a dissolver at a speed of 800 rpm. Then, the mixture was stirred with a dissolver at 800rpm for 20 minutes. Finally, the extender was transferred to a new jar.

As a result:

for printing on a white top liner, contact pressure was applied to a narrow format flexo printer (manufacturer: windmeyer and Hoelscher). The following were evaluated: the ink lay-out (lie) (1 very poor to 10 very good), the foam volume of the ink before and after storage (2 weeks at 50 ℃), the static surface tension of the ink and the colour value on the printed material were evaluated visually.

Both structures of the present invention were found to provide results comparable to typical substrate wetting agents available on the market in terms of lay-up, static surface tension and color value. It has been unexpectedly found that both structures of the present invention give better results in terms of foam properties than Surfynol 104H, which is known to be devoid of foam.

Example 19: evaluation of properties in Final stripe ink end use:

to prepare the test formulations, 30% of pigment base and 70% of extender are mixed and adjusted to a viscosity of 24-28 "(DIN 4 cup at 20 ℃) by adding water. The test formulations were applied by means of a laboratory contact pressure applicator (Erichsen Printing Proofer or

Labratester) or narrow format flexo printer (windmeyer and Hoelscher) to a variety of typical application substrates.

Formula of clear lacquer base TS 128/003

To prepare the clear binder, first, the liquid components are charged into a stainless steel container and heated to 70 ℃ by means of a hot plate with stirring (at a speed of 800rpm in a dissolver). Then, the solid resin was added to the mixture, which was then stirred with a dissolver at 800rpm until the solid resin had been sufficiently neutralized. The pH is checked periodically by means of a calibrated pH meter and, if necessary, more neutralizing agent is metered in. The target pH was 8.2-8.8.

Formulation of black pigment base (pigment Black 7)

To prepare the pigment base, first, the liquid component was charged into a wide-mouth glass bottle and stirred with a dissolver at a speed of 800rpm for 5 minutes. The pigment was then added to the mixture, followed by pre-dispersion with a dissolver at 3,000rpm for 20 minutes. Then, an equal amount of glass beads (diameter 2-2.5mm) was added to the mixture and the bottle was sealed and shaken in a Lau disperser (shaker) for 3 hours with 20% cooling. Finally, the glass beads were filtered off and the pigment base was transferred to a new jar.

Bulking agents

In order to be at commercial 80g/m²Office paper (Yes brand copy/print paper from UPM). The test formulations were applied by a laboratory contact pressure applicator (Erichsen Printing Proofer). The following were evaluated: the foam volume of the ink before and after storage (2 weeks at 50 ℃) and tiling of the ink on the printed material (1 ═ very poor to 10 ═ very good) was evaluated visually.

Substrate wetting agent	Tiling	Foam [ ml]	Foam after storage [ ml]
				Surfynol 104H	7	56	57
Wet 500	8	54	55
				Polyether from example 1	8	51	52
Polyether siloxanes from example 14	9	51	53
				Dynwet 800	8	52	53

In terms of tiling, both structures of the present invention were found to provide results comparable to typical substrate wetting agents available on the market. It has been unexpectedly found that both structures of the present invention give better results in terms of foam properties than Surfynol 104H, which is known to be devoid of foam.

Example 20: performance evaluation of gift wrapping paper end use:

to prepare the test formulations, 20% of pigment base and 80% of extender were mixed and adjusted by adding water to a viscosity of 16-18 "for gravure applications (DIN 4 cup at 20 ℃) or 12-25" for flexographic applications (DIN 4 cup at 20 ℃). The test formulations were applied by means of a laboratory contact pressure applicator (Erichsen Printing Proofer or

Formula of clear lacquer base TS 128/005

To prepare the clear binder, first, the liquid components are charged into a stainless steel container and heated to 70 ℃ by means of a hot plate with stirring (at a speed of 800rpm in a dissolver). Then, the solid resin was added to the mixture, which was then stirred with a dissolver at 800rpm until the solid resin had been sufficiently neutralized. The pH is checked periodically by means of a calibrated pH meter and, if necessary, further neutralizing agent is metered in. The target pH was 8.2-8.8.

Cyan pigment base (pigment blue 15:3) formulation

To prepare the pigment base, first, the liquid components were charged into a wide-mouth glass bottle and stirred with a dissolver at a speed of 800rpm for 5 minutes. The pigment was then added to the mixture, followed by pre-dispersion with a dissolver at 3,000rpm for 20 minutes. Then, an equal amount of glass beads (diameter 2-2.5mm) was added to the mixture and the bottle was sealed and shaken in a Lau disperser (shaker) for 3 hours with 20% cooling. Finally, the glass beads were filtered off and the pigment base was transferred to a new jar.

Bulking agents

To be at 80g/m of white²Soda paper (natron paper). Contact pressure applicator by laboratory: (

Labratester) contact pressure. The following were evaluated: the ink lay-out on the printed material (1-very poor to 10-very good), the foam volume of the ink before and after storage (2 weeks at 50 ℃) and the static surface tension of the ink were evaluated visually.

Example 21: performance evaluation of film packaging end use:

to prepare the test formulations, 10% of pigment base and 90% of extender are mixed and adjusted by adding water to a viscosity of 16-18 'for gravure applications (DIN 4 cup at 20 ℃) or 12-25' for flexographic applications (DIN 4 cup at 20 ℃). The test formulations were applied by means of a laboratory contact pressure applicator (Erichsen Printing Proofer or

Formula of clear lacquer base TS 128/003

Cyan pigment base (pigment blue 15:3) formulation

Bulking agents

For printing on white PE films with corona pretreatment. Contact pressure is applied to a narrow format flexo printing press (manufacturer: windmeeller and Hoelscher). The following were evaluated: the ink lay-up on the printed material (1-very poor to 10-very good), the foam volume of the ink before and after storage (2 weeks at 50 ℃), the static surface tension of the ink and the colour value were evaluated visually.

Both structures of the present invention were found to provide results comparable to or better than typical substrate wetting agents available on the market in terms of lay-up, static surface tension, foam properties and color values of the ink before and after storage.

Example 22: evaluation of properties of end-use applications of indian ink and writing ink:

to prepare the test formulations, 20% of pigment base and 80% of extender are mixed and adjusted to a viscosity of 22-25 "(DIN 4 cup at 20 ℃) by adding water. Contact pressure applicator for test formulations through the laboratory: (

Labratester) or a stylus (0.35 mm line width) from Rotring to a variety of typical application substrates.

Formula of clear lacquer base TS 128/005

To prepare the clear binder, first, the liquid components are charged into a stainless steel container and heated to 70 ℃ by a hot plate while stirring (at a speed of 800rpm in a dissolver). Then, the solid resin was added to the mixture, which was then stirred with a dissolver at 800rpm until the solid resin had been sufficiently neutralized. The pH is checked periodically by means of a calibrated pH meter and, if necessary, more neutralizing agent is metered in. The target pH was 8.2-8.8.

Formulation of black pigment base (pigment Black 7)

Bulking agents

In order to be at commercial 80g/m²Office paper (Yes brand copy/print paper available from UPM). The test formulation was applied by a Rotring stylus (line width 0.35 mm). The following were evaluated: the writing properties of the inks on the printed material (1-very poor to 10-very good) and the foam volume of the inks before and after storage (2 weeks at 50 ℃) were evaluated visually.

Substrate wetting agent	Tiling	Foam [ ml]	Foam after storage [ ml]
				Surfynol 104H	8	54	54
Wet 500	8	53	55
				Polyether from example 1	8	49	51
Polyether siloxanes from example 14	8	49	52
				Dynwet 800	8	50	52

In terms of tiling, both structures of the present invention were found to provide results comparable to typical substrate wetting agents available on the market. It has been unexpectedly found that the structures of the present invention give better results in terms of foam properties than Surfynol 104H, which is known to be devoid of foam.

Claims

1. Use of eugenol-based polyethers and/or reaction products of eugenol-based polyethers with siloxanes as wetting agents, wherein

The eugenol-based polyether corresponds to formula (I):

wherein

a＝1-1,000，

b＝0-1,000，

c＝0-1,000，

d＝0-1,000，

e＝1-10，

f＝0-500，

Provided that the sum of a + b + c + d + f is not less than 3, and

and, provided that the different monomer units of the segments having subscripts a, b and f can be in block structure with one another, wherein the individual blocks can be repeated a plurality of times and can be randomly distributed with respect to one another, or randomly distributed and also freely transposed with respect to one another, in the sense that they can be arranged in any desired order, with the proviso that the groups having subscripts c and d cannot follow one another or the other of the two,

and wherein

R¹Hydrogen or alkyl radicals having 1 to 8 carbon atoms,

R²hydrogen, an alkyl radical having 1 to 20 carbon atoms, or an aryl, or alkylaryl radical, independently of one another, or

R¹And a R²The radicals together forming a ring including R¹And R²The number of atoms to which they are bonded,

R³saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms,

R⁴、R⁷hydrogen and/or organic radicals, or R⁴And/or R⁷Is absent, wherein when R⁴And R⁷When not present, in R⁴And R⁷The position of the group is replaced by a C ═ C double bond,

the bridging Z-fragment may be present or absent,

wherein, in the absence of a bridging Z-fragment,

R⁵、R⁶independently of one another, hydrogen and/or organic radicals, wherein, when R is⁴And R⁷When one of the radicals is absent, the corresponding paired radical, i.e. when R is present⁴In the absence of R⁵And R⁷In the absence of R⁶Is an alkylidene group;

wherein, in the presence of the bridging Z segment,

R⁵、R⁶a hydrocarbyl group bridged cycloaliphatic or aromatic by a Z moiety, wherein Z is a divalent alkylene or alkenylene group, which is optionally further substituted,

R⁸、R⁹hydrogen, alkyl radicals having 1 to 20 carbon atoms, aryl radicals, alkylaryl radicals or alkoxy radicals,

R¹⁰hydrogen or an alkyl group having 1 to 8 carbon atoms or-c (o) -R¹¹or-C (O) -CH₂-C(O)-R¹²or-Si (R)¹³)₃or-C (O) -N- (R)¹⁴)₂OR-P (O) - (OR)¹⁹)₂Wherein

R¹¹、R¹²、R¹³Independently of one another, linear or branched, saturated or unsaturated, optionallyA further substituted alkyl, aryl or alkylaryl group having from 1 to 30 carbon atoms,

R¹⁸an allyl or 2-propenyl group, and

R¹⁹hydrogen, alkyl groups or polyether groups, independently of one another,

and wherein the one or more of the one,

the reaction product of the eugenol-based polyether and the siloxane corresponds to formula (II):

M_gM’ _hM” _nD_iD’_jD”_mT_kQ_lformula (II)

Wherein:

M＝[R¹⁵ ₃SiO_1/2]

M’＝[R¹⁶R¹⁵ ₂SiO_1/2]

M”＝[R¹⁷R¹⁵ ₂SiO_1/2]

D＝[R¹⁵ ₂SiO_2/2]

D’ ＝[R¹⁶R¹⁵SiO_2/2]

D”＝[R¹⁷R¹⁵SiO_2/2]

T＝[R¹⁵SiO_3/2]

Q＝[SiO_4/2]

g＝0-20，

h＝0-20，

i＝0-1,000，

j＝0-20，

k＝0-20，

l＝0-20，

m＝0-20，

n＝0-20，

provided that the sum of g + h + i + j + k +1+ m is not less than 3 and the sum of h + j is not less than 1,

and is

R¹⁵Independently of one another, identical or different hydrocarbyl radicals having 1 to 16 carbon atoms or H,

R¹⁶with the proviso that at least 10% of the radicals are eugenol-based polyether radicals which correspond to the general formula (III)

R¹⁷independently of one another, identical or different hydrocarbyl radicals having 1 to 16 carbon atoms and may also contain heteroatoms.

2. The use of claim 1, wherein R¹Hydrogen, methyl or ethyl.

3. The use of claim 1 or 2, wherein R²Hydrogen, methyl or ethyl.

4. The use of claim 1 or 2, wherein R¹And a R²The radicals may together form a ring including R¹And R²Bonded atoms, the ring containing 5 to 8 carbon atoms.

5. The use of claim 1 or 2, wherein R⁸、R⁹Is a methyl group.

6. The use of claim 1 or 2, wherein R¹⁰Is hydrogen, a methyl group, an acetyl group, -P (O) - (OR)¹⁹)₂or-C (O) -CH₂-C(O)-R¹²。

7. The use of claim 1 or 2, wherein R¹⁵Methyl and ethylA radical or a phenyl radical.

8. The use as claimed in claim 1 or 2, wherein, at R¹⁶In (b), the polyether group not based on eugenol corresponds to general formula (IV):

wherein the subscripts a to f and the group R¹-R¹⁰Is as defined in claim 1.

9. The use of claim 1 or 2, wherein R¹⁷With further substituents selected from SiC-bonded groups from allyl glycidyl ether, monoallyl glycidyl ether, allyl anisole, eugenol, hexenol, hexadecene and methylundecenoate.

10. Use according to claim 1 as a substrate wetting agent.

11. Use according to claim 1 or 2 as a substrate wetting agent in printing inks, printing varnishes and/or other inks or varnishes which can be applied using analogue or digital coating methods.

12. Use according to claim 1 or 2 as a substrate wetting agent for printing films, paper, cards, cardboard, folding boxes, bags, wood surfaces, metal surfaces, plastic surfaces, glass and/or ceramics.

13. Use according to claim 1 or 2 as a substrate wetting agent for wallpaper.

14. Use according to claim 1 or 2 as a substrate wetting agent for sacks.

15. Use according to claim 1 or 2 as a substrate wetting agent for hygiene paper.

16. Use according to claim 1 or 2 as a substrate wetting agent for beverage cartons.

17. Use according to claim 1 or 2 as a substrate wetting agent for boards.

18. Use according to claim 1, characterized in that the eugenol-based polyether of formula (I) is prepared by double metal cyanide catalysis.

19. Use according to claim 1, characterized in that the eugenol-based polyether of formula (I) is prepared by alkaline catalysis.

20. Use according to claim 1, wherein the reaction product of the eugenol-based polyether of formula (II) with the siloxane is obtained by double metal cyanide-catalyzed preparation of the eugenol-based polyether of formula (I) and subsequent reaction therewith with a Si-H functional siloxane.

21. A composition comprising:

a) at least one compound of the formula (I) or (II) as claimed in claim 1 for use as wetting agent, and

c) at least one binder.

22. The composition of claim 21, further comprising e) at least one solvent.

23. The composition of claim 21, further comprising e) at least one solvent selected from water, ethanol, isopropanol, and/or ethyl acetate.

24. The composition of claim 21 or 22, further comprising b) one or more pigments and fillers.

25. The composition of claim 24, wherein the pigment is selected from pigment white 6, pigment black 7, pigment blue 15:3, pigment blue 15:4, pigment red 57:1, pigment yellow 12, pigment yellow 13, pigment violet 23, and/or pigment green 7.

26. The composition of claim 21 or 22, further comprising h) one or more defoamers.

27. The composition of claim 21 or 22, comprising:

a) 0.1% to 20% by weight of at least one compound of the formula (I) or (II),

b) 0.0% to 75% by weight of at least one pigment,

c) 0.5-80% by weight of at least one binder,

d) 0.0% to 10% by weight of at least one wax,

e) 0.5-80% by weight of at least one solvent,

f) 0.5% to 70% by weight of at least one film-forming auxiliary,

g) 0.0% to 10% by weight of at least one rheological additive,

h) 0.0% to 5% by weight of at least one defoamer,

i) 0.0% to 15% by weight of at least one neutralizing agent,

j) 0.0% to 25% by weight of other components,

wherein the sum of all components taken together is 100 weight percent and all weight percents are based on the total weight of the composition.

28. The composition of claim 21 or 22, comprising:

a) 0.5% to 1.5% by weight of at least one compound of the formula (I) or (II),

b) 2% to 50% by weight of at least one pigment,

c) 2-40% by weight of at least one binder,

d) 0.5-5% by weight of at least one wax,

e) 10-60% by weight of at least one solvent,

f) 1-10% by weight of at least one film-forming auxiliary,

g) 0.2-5% by weight of at least one rheological additive,

h)0.05 to 2% by weight of at least one defoamer,

i)0.1 to 10% by weight of at least one neutralizing agent,

j) 0% to 10% by weight of other components,